RU2009105477A - METHOD FOR PRODUCING WATER-ABSORBING POLYMER PARTICLES WITH HIGH PERMEABILITY BY POLYMERIZATION DROPS OF MONOMERIC SOLUTION - Google Patents

METHOD FOR PRODUCING WATER-ABSORBING POLYMER PARTICLES WITH HIGH PERMEABILITY BY POLYMERIZATION DROPS OF MONOMERIC SOLUTION Download PDF

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RU2009105477A
RU2009105477A RU2009105477/15A RU2009105477A RU2009105477A RU 2009105477 A RU2009105477 A RU 2009105477A RU 2009105477/15 A RU2009105477/15 A RU 2009105477/15A RU 2009105477 A RU2009105477 A RU 2009105477A RU 2009105477 A RU2009105477 A RU 2009105477A
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polymer particles
water
monomer
absorbing polymer
microns
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RU2463309C2 (en
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Уве ШТЮЕН (DE)
Уве ШТЮЕН
Маттиас ВАЙСМАНТЕЛЬ (DE)
Маттиас ВАЙСМАНТЕЛЬ
Вильфрид ХАЙДЕ (DE)
Вильфрид ХАЙДЕ
Марко КРЮГЕР (DE)
Марко Крюгер
Фолькер ЗАЙДЛЬ (DE)
Фолькер Зайдль
Штефан БЛЯЙ (DE)
Штефан БЛЯЙ
Деннис ЛЕШ (DE)
Деннис ЛЕШ
Рюдигер ФУНК (DE)
Рюдигер ФУНК
Аннемари ХИЛЛЕБРЕХТ (DE)
Аннемари ХИЛЛЕБРЕХТ
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Басф Се (De)
Басф Се
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2989—Microcapsule with solid core [includes liposome]

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Polymerisation Methods In General (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

1. Способ получения водопоглощающих полимерных частиц путем полимеризации капель мономерного раствора, содержащего ! a) по меньшей мере, один этилен-ненасыщенный мономер, ! b) по меньшей мере, один сшиватель, ! c) по меньшей мере, один инициатор, ! d) воду ! в окружающей капли газовой фазе, отличающийся тем, что в мономерном растворе суспендируют не растворимую в воде неорганическую соль, и полимерные частицы имеют средний диаметр, по меньшей мере, 150 мкм. ! 2. Способ по п.1, отличающийся тем, что мономер а) имеет, по меньшей мере, одну кислотную группу. ! 3. Способ по п.2, отличающийся тем, что кислотные группы мономеров а) являются, по меньшей мере, частично нейтрализованными. ! 4. Способ по п.1, отличающийся тем, что мономером а) до, по меньшей мере, 50% моль, является акриловая кислота. ! 5. Способ по п.1, отличающийся тем, что полимерные частицы имеют средний диаметр, по меньшей мере, 200 мкм. ! 6. Способ по п.1, отличающийся тем, что, по меньшей мере, 90 мас.%, полимерных частиц имеют диаметр от 100 до 800 мкм. ! 7. Способ по п.1, отличающийся тем, что газ-носитель протекает через реакционное пространство. ! 8. Способ по п.7, отличающийся тем, что газ-носитель, покидающий реакционное пространство, после прохождения возвращают, по меньшей мере, частично. ! 9. Способ по п.7, отличающийся тем, что содержание кислорода газа-носителя составляет от 0,001 до 0,15 об.%. ! 10. Способ по одному из пп.1-9, отличающийся тем, что полученные полимерные частицы сушат и/или дополнительно сшивают на, по меньшей мере, одной следующей стадии способа. ! 11. Водопоглощающие полимерные частицы, причем полимерные частицы имеют среднюю сферичность, по меньшей мере, 0,84, содержание гидрофобн 1. A method of obtaining water-absorbing polymer particles by polymerization of drops of a monomer solution containing! a) at least one ethylenically unsaturated monomer,! b) at least one stapler,! c) at least one initiator,! d) water! in the gas phase surrounding the droplet, characterized in that a water-insoluble inorganic salt is suspended in the monomer solution, and the polymer particles have an average diameter of at least 150 μm. ! 2. A method according to claim 1, characterized in that the monomer a) has at least one acidic group. ! 3. A process according to claim 2, characterized in that the acid groups of the monomers a) are at least partially neutralized. ! 4. The method according to claim 1, characterized in that the monomer a) up to at least 50 mol% is acrylic acid. ! 5. A method according to claim 1, wherein the polymer particles have an average diameter of at least 200 microns. ! 6. The method according to claim 1, characterized in that at least 90 wt.% Of the polymer particles have a diameter of from 100 to 800 microns. ! 7. A method according to claim 1, wherein the carrier gas flows through the reaction space. ! 8. A method according to claim 7, characterized in that the carrier gas leaving the reaction space is at least partially returned after passing through. ! 9. The method according to claim 7, characterized in that the oxygen content of the carrier gas is from 0.001 to 0.15 vol.%. ! 10. A method according to one of claims 1 to 9, characterized in that the resulting polymer particles are dried and / or additionally crosslinked in at least one subsequent process step. ! 11. Water-absorbing polymer particles, and the polymer particles have an average sphericity of at least 0.84, the content is hydrophobic

Claims (20)

1. Способ получения водопоглощающих полимерных частиц путем полимеризации капель мономерного раствора, содержащего1. The method of obtaining water-absorbing polymer particles by polymerization of drops of a monomer solution containing a) по меньшей мере, один этилен-ненасыщенный мономер,a) at least one ethylene unsaturated monomer, b) по меньшей мере, один сшиватель,b) at least one stapler, c) по меньшей мере, один инициатор,c) at least one initiator, d) водуd) water в окружающей капли газовой фазе, отличающийся тем, что в мономерном растворе суспендируют не растворимую в воде неорганическую соль, и полимерные частицы имеют средний диаметр, по меньшей мере, 150 мкм.in the gas phase surrounding the droplet, characterized in that an inorganic salt insoluble in water is suspended in the monomer solution, and the polymer particles have an average diameter of at least 150 μm. 2. Способ по п.1, отличающийся тем, что мономер а) имеет, по меньшей мере, одну кислотную группу.2. The method according to claim 1, characterized in that the monomer a) has at least one acid group. 3. Способ по п.2, отличающийся тем, что кислотные группы мономеров а) являются, по меньшей мере, частично нейтрализованными.3. The method according to claim 2, characterized in that the acid groups of the monomers a) are at least partially neutralized. 4. Способ по п.1, отличающийся тем, что мономером а) до, по меньшей мере, 50% моль, является акриловая кислота.4. The method according to claim 1, characterized in that the monomer a) to at least 50% mol, is acrylic acid. 5. Способ по п.1, отличающийся тем, что полимерные частицы имеют средний диаметр, по меньшей мере, 200 мкм.5. The method according to claim 1, characterized in that the polymer particles have an average diameter of at least 200 microns. 6. Способ по п.1, отличающийся тем, что, по меньшей мере, 90 мас.%, полимерных частиц имеют диаметр от 100 до 800 мкм.6. The method according to claim 1, characterized in that at least 90 wt.%, The polymer particles have a diameter of from 100 to 800 microns. 7. Способ по п.1, отличающийся тем, что газ-носитель протекает через реакционное пространство.7. The method according to claim 1, characterized in that the carrier gas flows through the reaction space. 8. Способ по п.7, отличающийся тем, что газ-носитель, покидающий реакционное пространство, после прохождения возвращают, по меньшей мере, частично.8. The method according to claim 7, characterized in that the carrier gas leaving the reaction space is returned at least partially after passage. 9. Способ по п.7, отличающийся тем, что содержание кислорода газа-носителя составляет от 0,001 до 0,15 об.%.9. The method according to claim 7, characterized in that the oxygen content of the carrier gas is from 0.001 to 0.15 vol.%. 10. Способ по одному из пп.1-9, отличающийся тем, что полученные полимерные частицы сушат и/или дополнительно сшивают на, по меньшей мере, одной следующей стадии способа.10. The method according to one of claims 1 to 9, characterized in that the obtained polymer particles are dried and / or additionally crosslinked in at least one next stage of the method. 11. Водопоглощающие полимерные частицы, причем полимерные частицы имеют среднюю сферичность, по меньшей мере, 0,84, содержание гидрофобного растворителя, меньше, чем 0,005 мас.%, и проницаемость, по меньшей мере, 5·10-7 см3 с/г.11. Water-absorbing polymer particles, the polymer particles having an average sphericity of at least 0.84, a hydrophobic solvent content of less than 0.005 wt.%, And a permeability of at least 5 · 10 -7 cm 3 s / g . 12. Водопоглощающие полимерные частицы по п.11, отличающиеся тем, что полимерные частицы имеют емкость центрифугального удержания, по меньшей мере, 10 г/г.12. Water-absorbing polymer particles according to claim 11, characterized in that the polymer particles have a centrifugal retention capacity of at least 10 g / g 13. Водопоглощающие полимерные частицы по п.11, отличающиеся тем, что полимерные частицы имеют средний диаметр, по меньшей мере, 200 мкм.13. Water-absorbing polymer particles according to claim 11, characterized in that the polymer particles have an average diameter of at least 200 microns. 14. Водопоглощающие полимерные частицы по п.11, отличающиеся тем, что, по меньшей мере, 90 мас.%, полимерных частиц имеют средний диаметр от 100 до 800 мкм.14. Water-absorbing polymer particles according to claim 11, characterized in that at least 90 wt.%, The polymer particles have an average diameter of from 100 to 800 microns. 15. Водопоглощающие полимерные частицы по п.11, отличающиеся тем, что полимерные частицы, по меньшей мере, частично состоят из полимеризуемого этилен-ненасыщенного мономера, несущего группы кислот.15. The water-absorbing polymer particles according to claim 11, characterized in that the polymer particles at least partially consist of a polymerizable ethylene-unsaturated monomer carrying acid groups. 16. Водопоглощающие полимерные частицы по п.15, отличающиеся тем, что группы кислот полимеризуемого мономера являются, по меньшей мере, частично нейтрализованными.16. The water-absorbing polymer particles according to clause 15, wherein the acid groups of the polymerizable monomer are at least partially neutralized. 17. Водопоглощающие полимерные частицы по п.15, отличающиеся тем, что этилен-ненасыщенный мономер до, по меньшей мере, 50 мол.% является акриловой кислотой.17. Water-absorbing polymer particles according to clause 15, wherein the ethylenically unsaturated monomer to at least 50 mol.% Is acrylic acid. 18. Полимерные частицы по одному из пп.11-17, отличающиеся тем, что полимерные частицы содержат не растворимые в воде неорганические соли.18. The polymer particles according to one of paragraphs.11-17, characterized in that the polymer particles contain water-insoluble inorganic salts. 19. Применение полимерных частиц по одному из пп.11-18 для получения предметов санитарии и гигиены.19. The use of polymer particles according to one of paragraphs.11-18 for obtaining items of sanitation and hygiene. 20. Предметы санитарии и гигиены, содержащие полимерные частицы по одному из пп.11-18. 20. Sanitary and hygiene items containing polymer particles according to one of paragraphs.11-18.
RU2009105477/04A 2006-07-19 2007-07-12 Method of producing water-absorbing polymer particles with high permeability by polymerising droplets of monomer solution RU2463309C2 (en)

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